WO2021182378A1

WO2021182378A1 - Surface-coated inorganic particles, method for producing same, and organic-solvent dispersion of same

Info

Publication number: WO2021182378A1
Application number: PCT/JP2021/008927
Authority: WO
Inventors: 加藤　大典; 理人滝本
Original assignee: 石原産業株式会社
Priority date: 2020-03-10
Filing date: 2021-03-08
Publication date: 2021-09-16
Also published as: CN115279840B; US20240209213A1; KR20220147608A; CN115279840A; TW202204527A; EP4119617A1; JPWO2021182378A1

Abstract

Provided are: surface-coated inorganic particles which can have improved dispersibility in organic solvents and enable the function and performance of the original inorganic particles to be sufficiently exhibited; and a method for producing the surface-coated inorganic particles. Also provided are an organic-solvent dispersion and a coating film which are excellent in terms of transparency and refraction property.　The surfaces of inorganic particles, e.g., titanium oxide, are coated with a product of reaction between an aminated silicate compound, e.g., aminopropyltrimethoxysilane, and/or a product of the hydrolysis thereof and a compound having one α,β-unsaturated carbonyl group in the molecule, e.g., an alkoxypolyalkylene glycol (meth)acrylate.

Description

Surface-coated inorganic particles, a method for producing the same, and an organic solvent dispersion in which the particles are dispersed.

The present invention relates to surface-coated inorganic particles and a method for producing the same, an organic solvent dispersion in which the particles are dispersed and a method for producing the same, a coating composition containing the same, and a method for producing a surface-coated inorganic particle layer.

Various inorganic particles such as metal oxides, metal nitrides, and metals are used in various applications such as pigments, ultraviolet shielding agents, infrared shielding agents, visible light transmitting agents, fillers, hard coating agents, and refractive index adjusting agents. There is. At that time, in order to enhance the dispersibility in the dispersion medium and the functions such as shielding property and permeability, the surface may be coated with an organic compound and used. For example, Patent Document 1 discloses metal oxide core particles having a coating layer containing an inorganic substance, (i) a quaternary silane coupling agent and / or (ii) a silane coupling agent, and a hydrophobic agent. It is described that an aminosilane coupling agent is specifically used as a silane coupling agent to exhibit effective UV absorption characteristics, reduced photoactivity, and improved skin feel.
Further, Patent Document 2 describes an alkoxysilyl obtained by reacting an aminosilane compound (a) containing a primary or secondary amino group and an alkoxysilyl group with a compound (b) having at least two unsaturated double bonds. A method for producing polymerizable particles, which comprises reacting a compound (c) having a group and an unsaturated double bond with a metal oxide particle (d) having a functional group capable of reacting with an alkoxysilyl group on the surface. Is disclosed.

Japanese Patent Application Laid-Open No. 2015-531743 Japanese Unexamined Patent Publication No. 2005-220243

In Patent Document 1 described above, by having a coating layer containing an aminosilane coupling agent, the dispersibility of the surface coating particles in the dispersion medium is improved from the level at that time, but at present, further improvement is required. Has been done. Further, when the organic-inorganic composite particles described in Patent Document 2 are used as a coating agent, a cured coating film having better transparency, scratch resistance, hardness, solvent resistance, and adhesion than those at that time is produced. However, at present, there is a need for the development of new surface-coated particles capable of providing organic solvent dispersions and coating films with further improved transparency and refraction.

In order to improve the dispersibility of inorganic particles coated with an organic compound in an organic solvent, the present inventors have conducted intensive studies and found that a silicate compound having an amino group has one α, β-unsaturated carbonyl group in the molecule. When the surface of the inorganic particles is coated with the product reacted with the compound having the above, the desired dispersibility in the organic solvent can be obtained, and the organic solvent dispersion or coating film of the obtained surface-coated inorganic particles can be obtained. Has found that it can be made excellent in transparency and refractive property, and completed the present invention.

That is, the present invention
(1) A surface-coated inorganic particle in which the surface of an inorganic particle is coated with a reaction product of a silicate compound having an amino group and / or a hydrolysis product thereof and a compound having one α, β-unsaturated carbonyl group in the molecule. particle,
(2) The surface-coated inorganic particles according to (1), wherein the compound having an α, β-unsaturated carbonyl group is a compound having an ether bond.
(3) The compound having an α, β-unsaturated carbonyl group is an ethylene glycol chain (polymerization number n = 2 to 10), a propylene glycol chain (polymerization number n = 2 to 10), or a 5- to 6-membered cyclic group. The surface-coated inorganic particles according to (1) or (2), which is a compound having
(4) The compounds having an α, β-unsaturated carbonyl group are (meth) acrylates having a 5- to 6-membered cyclic group or alkoxypolyalkylene glycol (meth) acrylates, (1) to (3). ), The surface-coated inorganic particles according to any one of the above.
(5) The compound having an α, β-unsaturated carbonyl group is tetrahydrofurfuryl acrylate, methoxytriethylene glycol acrylate, methoxypolyethylene glycol acrylate or methoxydipropylene glycol acrylate, according to (1) to (4). Surface coated inorganic particles according to any one,
(6) When the amino group of the silicate compound having an amino group and / or its hydrolysis product in the reaction product is a mol and the compound having an α, β-unsaturated carbonyl group is b mol, it is 0. The surface-coated inorganic particles according to any one of (1) to (5), wherein 8 ≦ a / b ≦ 10.
(7) The surface-coated inorganic particles according to any one of (1) to (6), wherein the reaction product is a small molecule silicate compound having 3 to 100 carbon atoms and / or a hydrolysis product thereof.
(8) The surface-coated inorganic particles according to any one of (1) to (7), wherein the inorganic particles are composed of inorganic core particles and an inorganic compound coated on the surface thereof.
(9) Surface-coated inorganic particles, wherein the inorganic particles according to any one of (1) to (7) or the inorganic core particles according to (8) are titanium oxide particles.
(10) An organic solvent dispersion of surface-coated inorganic particles in which the surface-coated inorganic particles according to any one of (1) to (9) are dispersed in an organic solvent.
(11) A coating composition containing the surface-coated inorganic particles according to any one of (1) to (9), an organic solvent, and a resin.
(12) A coating composition containing the organic solvent dispersion according to (10) and a resin.
(13) The inorganic particles are mixed with the silicate compound having an amino group and / or the hydrolysis product thereof in an aqueous solvent, and the silicate compound having an amino group on the surface of the inorganic particles and / or the hydrolysis product thereof. The first step of coating and
Next, after replacing the aqueous solvent with an organic solvent, a compound having one α, β-unsaturated carbonyl group in the molecule is mixed, and the silicate compound having an amino group coated on the surface of the inorganic particles and the silicate compound. / Or a second step of coating the surface of the inorganic particles with a reaction product of the hydrolysis product thereof and the compound having an α, β-unsaturated carbonyl group.
Method for producing surface-coated inorganic particles, including
(14) In the second step, the surfactant and the organic solvent are mixed with the aqueous solvent, the inorganic particles are transferred to the organic solvent, the organic solvent is replaced with the aqueous solvent, and then the α, β- The method for producing a surface-coated inorganic particle according to (13), wherein a compound having an unsaturated carbonyl group is mixed.
(15) Inorganic particles, a silicate compound having an amino group and / or a hydrolysis product thereof, and a compound having one α, β-unsaturated carbonyl group in the molecule are mixed to obtain the above amino group. A method for producing a surface-coated inorganic particle, which comprises coating the surface of the inorganic particle with a reaction product of the silicate compound and / or a hydrolysis product thereof and the compound having an α, β-unsaturated carbonyl group.
(16) When the amino group of the silicate compound having an amino group and / or its hydrolysis product is a mol, and the compound having an α, β-unsaturated carbonyl group is b mol, 0.8 ≦ The method for producing a surface-coated inorganic particle according to any one of (13) to (15), wherein a / b ≦ 10.
(17) A third step of adding a poor solvent to the organic solvent dispersion obtained in the second step according to (13) or (14), solid-liquid separation, and recovering the surface-coated inorganic particles.
Next, a fourth step of dispersing the recovered surface-coated inorganic particles in an organic solvent, and
Method for Producing Organic Solvent Dispersion of Surface-Coated Inorganic Particles, Containing
(18) In an organic solvent, inorganic particles, a silicate compound having an amino group and / or a hydrolysis product thereof, and a compound having one α, β-unsaturated carbonyl group in the molecule are mixed. The reaction product of the silicate compound having an amino group and / or its hydrolysis product and the compound having an α, β-unsaturated carbonyl group is coated on the surface of the inorganic particles and dispersed in the organic solvent. , A method for producing an organic solvent dispersion of surface-coated inorganic particles,
(19) When the amino group of the silicate compound having an amino group and / or its hydrolysis product is a mol, and the compound having an α, β-unsaturated carbonyl group is b mol, 0.8 ≦ The method for producing an organic solvent dispersion according to (18), wherein a / b ≦ 10.
(20) A method for producing a surface-coated inorganic particle layer, wherein the organic solvent dispersion of the surface-coated inorganic particles according to (10) or the coating composition according to (11) or (12) is applied or sprayed onto a substrate.
And so on.

INDUSTRIAL APPLICABILITY According to the present invention, the dispersibility of the inorganic particles in an organic solvent can be sufficiently improved, whereby the functions and performances of the inorganic particles can be sufficiently exhibited.
In addition, the organic solvent dispersion or coating film of the surface-coated inorganic particles obtained by the present invention may also provide better transparency and refraction than the organic solvent dispersion or coating film of conventional surface-coated inorganic particles. It is possible.
Further, the surface-coated inorganic particles of the present invention and the organic solvent dispersion thereof can be produced by a simple method.

In the present invention, the surface of an inorganic particle is coated with a reaction product of a silicate compound having an amino group and / or a hydrolysis product thereof and a compound having one α, β-unsaturated carbonyl group in the molecule. It is an inorganic particle.

The inorganic particles are not particularly limited, and are, for example, metal oxide particles such as zinc oxide, titanium oxide, zirconium oxide, tin oxide, cerium oxide, iron oxide, and silicon oxide, barium titanate, strontium titanate, calcium titanate, and the like. Metal composite oxide particles, metal nitrides such as titanium nitride, titanium oxynitride, silicon nitride, silicon oxynitride, aluminum nitride, aluminum oxynitride, metal carbides such as titanium carbide, zirconium carbide, silicon carbide, aluminum carbide, etc. Examples include metal compound particles and metal particles such as metallic copper, silver and gold. The average particle size of the inorganic particles can be appropriately designed according to the application, and is preferably in the range of 1 nm to 50 μm (that is, 1 nm or more and 50 μm or less), and more preferably 2 nm to 5 μm (that is, 2 nm or more and 5 μm). It is more preferably 3 nm to 500 nm (that is, 3 nm or more and 500 nm or less), and most preferably 3 nm to 100 nm (that is, 3 nm or more and 100 nm or less). The average particle size is a numerical value obtained by measuring 100 longest linear portions from an electron micrograph of inorganic particles and averaging the number of these measured values.

The inorganic particles may be composed of the inorganic particles themselves, or may be composed of the inorganic core particles and the inorganic compound coated on the surface thereof. Examples of the inorganic core particles include the above-mentioned inorganic particles such as titanium oxide, zinc oxide, silicon oxide, and aluminum oxide, and the surface of the particles is oxides such as silicon, aluminum, tin, zinc, titanium, antimony, and zirconium, and water. Those coated with an inorganic compound such as an oxide are preferable. When the inorganic particles are composed of the inorganic particles themselves, the inorganic particles are preferably titanium oxide particles. When the inorganic particles are composed of the inorganic core particles and the inorganic compound coated on the surface thereof, the inorganic core particles are preferably titanium oxide particles. The coating with an inorganic compound means a state in which the inorganic compound is present on the surface of the inorganic core particles by adsorbing or precipitating the inorganic compound on the surface of the inorganic core particles. The coating with the inorganic compound may be in a state where the inorganic compound is present on at least a part of the surface of the inorganic particles. The coating amount of the inorganic compound is preferably 0.1 to 50 parts by mass (that is, 0.1 parts by mass or more and 50 parts by mass or less) with respect to 100 parts by mass of the inorganic particles, and 0.5 to 40 parts by mass (that is, that is). 0.5 parts by mass or more and 40 parts by mass or less) is more preferable, and 1 to 30 parts by mass (that is, 1 part by mass or more and 30 parts by mass or less) is further preferable. The surface of the inorganic core particles of titanium oxide is preferably coated with an oxide such as silicon, aluminum, tin, zinc, titanium, antimony, zirconium or an inorganic compound such as hydroxide, and a titanium dioxide pigment or titanium oxide fine particles. It can be used for such purposes. When used as a titanium dioxide pigment, the average particle size is preferably 0.1 μm to 0.5 μm (that is, 0.1 μm or more and 0.5 μm or less), and 0.15 μm to 0.4 μm (that is, 0.15 μm or more and 0.4 μm or less). The following) is more preferable, and 0.2 μm to 0.3 μm (0.2 μm or more and 0.3 μm or less) is further preferable. When used as titanium oxide fine particles, the average particle size is preferably 1 nm to 100 nm (that is, 1 nm or more and 100 nm or less), more preferably 2 nm to 80 nm (that is, 2 nm or more and 80 nm or less), and 3 nm to 50 nm (that is, 3 nm or more and 50 nm or less). ) Is more preferable.

The reactant coated on the surface of the inorganic particles is obtained by reacting a silicate compound having an amino group and / or a hydrolysis product thereof with a compound having one α, β-unsaturated carbonyl group in the molecule. .. Such a reaction is called a Michael addition reaction and is a mono-α, β-unsaturated carbonyl compound having one C = C bond in the molecule (that is, having one α, β-unsaturated carbonyl group in the molecule). This is a reaction in which a silicate compound having an amino group is added to a compound). For this reason, the reactant may be referred to as a Michael adduct. The reaction product is understood to be a compound in which a silicate compound and / or a hydrolysis product thereof is added via an amino group to a compound having one α, β-unsaturated carbonyl group in the molecule. The Michael addition reaction is preferably carried out in the presence of the inorganic particles, and the produced Michael adduct can be coated on the surface of the inorganic particles. _{In the Michael addition reaction, among the amino groups (NH 2} ) contained in the silicate compound and / or its hydrolysis product, the hydrogen of the amino group does not remain, that is, two hydrogens of the amino group are α, β-non. A reaction may be carried out in which hydrogen of an amino group does not remain after being added to 2 mol of a compound having a saturated carbonyl group, but a reaction in which hydrogen (NH) of an amino group remains, that is, one hydrogen of an amino group is α, β-unsaturated carbonyl. A reaction in which 1 mol of a compound having a group is added and one hydrogen of an amino group remains is preferable. Therefore, assuming that the amino group of the silicate compound having an amino group and / or its hydrolysis product is a mol, and the compound having one α, β-unsaturated carbonyl group in the molecule is b mol, 0.8 ≦ The reaction at a molar ratio such that a / b ≦ 10 is preferable, 1 ≦ a / b ≦ 10 is more preferable, 1 ≦ a / b ≦ 8 is more preferable, and 1 ≦ a / b ≦ 6 is most preferable.

Specific examples of the silicate compound having an amino group include _{a silanol compound of -C-Si (OH) 3,} an alkoxysilane compound of -C-Si (OR) ₃ , and -C-Si (OR) _x R'3 _-x. Alkoxyalkoxysilane compounds (x is an integer of 1 to 3 (that is, 1 or more and 3 or less)) and the like, and those containing a hydrolyzable group such as an alkoxy group represented by the following general formula (1) are more preferable.

In the general formula (1), x represents an integer of 1 to 3 (that is, 1 or more and 3 or less), y represents an integer of 0 to 2 (that is, 0 or more and 2 or less), and z represents 0 to 1 (that is, 0 to 1 (that is, 0 or more and 2 or less). That is, it represents an integer of 0 or 1). However, x + y + z = 3. R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (that is, 1 or more and 4 or less).

Specific examples of the silicate compound having an amino group include an amino group-containing alkoxysilane and an amino group-containing di (alkoxysilane), and examples of the former include 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane. , 3-Aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxy Silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, 3- (trimethoxysilylpropyl) aminopropyltrimethoxysilane , 3- (Triethoxysilylpropyl) Aminopropyltriethoxysilane, 2- (Trimethoxysilylpropyl) Aminoethyl-3-aminopropyltrimethoxysilane, 2- (Triethoxysilylpropyl) Aminoethyl-3-aminopropyltri Examples thereof include ethoxysilane. Further, examples of the latter include bis (trimethoxysilylpropyl) amine, and hydrolysis products thereof can be prepared and used.

The compound having one α, β-unsaturated carbonyl group in the molecule is not particularly limited as long as it is a mono-α, β-unsaturated carbonyl compound having one C = C bond in the molecule, and is generally described below. Those having a skeleton represented by the formula (2) are preferable. Further, the compound having one α, β-unsaturated carbonyl group in the molecule is more preferably a compound having an ether bond in the molecule, and the compound having an ether bond has a polymerization number of n = 2 to 10. (That is, 2 or more and 10 or less) ethylene glycol chain, polymerization number n = 2 to 10 (that is, 2 or more and 10 or less) propylene glycol chain or 5 to 6-membered cyclic group (that is, 5 or 6-membered cyclic group) The compound having the compound is more preferable, and (meth) acrylates having a 5- to 6-membered cyclic group or alkoxypolyalkylene glycol (meth) acrylates are further preferable. The term "(meth) acrylate" means acrylate and / or methacrylate (sometimes referred to as methacrylate).

In the above general formula (2), R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (that is, 1 or more and 4 or less).

Specific examples of the compound having one α, β-unsaturated carbonyl group in the molecule include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n. -Alkyl (meth) acrylates such as butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate; Cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol ( (Meta) acrylates having a 5- to 6-membered cyclic group such as meta) acrylate; methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) Alkoxypolyalkylene glycol (meth) acrylates such as acrylates, methoxypolypropylene glycol (meth) acrylates and ethoxypolyethylene glycol (meth) acrylates; 2-hydroxyethyl (meth) acrylates, 2-hydroxypropyl (meth) acrylates, 2-hydroxy Hydroxyl-containing (meth) acrylates such as butyl (meth) acrylate, glycerol (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate; (meth) acrylamide, N, N-dimethyl (meth) acrylamide. , N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, N-substituted (meth) acrylamides such as acryloylmorpholin; N, N-dimethylaminoethyl (meth) acrylate , N, N-diethylaminoethyl (meth) acrylate and other amino group-containing (meth) acrylates; and the like. Further, in addition to the above-mentioned compounds, polyester (meth) acrylate, polyurethane (meth) acrylate, epoxy (meth) acrylate, (meth) acrylicized maleic acid-modified polybutadiene and the like can be mentioned. Among these, (meth) acrylates having a 5- to 6-membered cyclic group or alkoxypolyalkylene glycol (meth) acrylates are preferable, and tetrahydrofurfuryl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, and methoxypolyethylene glycol are preferable. (Meta) acrylate or methoxydipropylene glycol (meth) acrylate is more preferable, and among the more preferable ones, tetrahydrofurfuryl acrylate (hereinafter, may be referred to as "THF-A") and methoxytriethylene glycol acrylate which are acrylates. (Hereinafter, it may be referred to as "methoxy-triethylene glycol acrylate" or "MTG-A"), methoxypolyethylene glycol acrylate (hereinafter, may be referred to as "130A") or methoxydipropylene glycol acrylate (hereinafter, may be referred to as "130A"). Hereinafter, it may be described as "methoxydipropylene glycol acrylate" or "DPM-A"), which is most preferable.

When the reaction product is coated on the surface of the inorganic particles, the reaction product or a part of the reaction product is deformed due to the reaction product adsorbing, precipitating, or reacting on the surface of the inorganic particles. (For example, the alkoxy group is decomposed, separated into an alkyl group and a hydroxyl group, and adsorbed on the inorganic particles by the hydroxyl group (-Si-OH-), or the reaction product is hydrolyzed on the surface of the inorganic particles. It means that it exists in the state of existence). The reaction product is preferably a low molecular weight silicate compound having 3 to 100 carbon atoms (that is, 3 or more and 100 or less) and / or a hydrolysis product thereof, and more preferably 3 to 50 carbon atoms (that is, 3 or more and 50 or less). More preferably, the number of carbon atoms is 3 to 40 (that is, 3 or more and 40 or less).

The reaction product may be coated as long as it is present on at least a part of the surface of the inorganic particles, and in order to sufficiently disperse the inorganic particles in the organic solvent, it is preferable to coat the reaction product as densely as possible. The coating amount is preferably 0.1 to 50 parts by mass (that is, 0.1 parts by mass or more and 40 parts by mass or less) with respect to 100 parts by mass of the inorganic particles, and 0.5 to 40 parts by mass (that is, 0.5 parts by mass). It is more preferably 1 to 30 parts by mass (that is, 1 part by mass or more and 30 parts by mass or less).

Next, a dispersion in which the surface-coated inorganic particles are dispersed in an organic solvent will be described. In the present application, the dispersion in which the surface-coated inorganic particles are dispersed in an organic solvent is referred to as an organic solvent dispersion, and the organic solvent can be appropriately selected, and specifically, toluene, xylene, solvent naphtha, normal hexane. , Isohexane, cyclohexane, methylcyclohexane, normal heptane, tridecane, tetradecane, pentadecane and other hydrocarbon solvents; methanol, EtOH (ethanol), butanol, IPA (isopropyl alcohol), normal propyl alcohol, 2-butanol, TBA (terrific) Alcohol-based solvents such as butanol), butanediol, ethylhexanol, and benzyl alcohol; ketone solvents such as acetone, MEK (methylethylketone), methylisobutylketone, DIBK (diisobutylketone), cyclohexanone, DAA (diacetone alcohol); ethyl acetate , Butyl acetate, methoxybutyl acetate, cellosolve acetate, amyl acetate, normal propyl acetate, isopropyl acetate, methyl lactate, ethyl lactate, butyl lactate, γ-butyl lactone and other ester-based media; methyl cellosolve, cellosolve, butyl cellosolve, dioxane, Ether solvents such as MTBE (methyl tertiary butyl ether) and butyl carbitol; glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol and propylene glycol; diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, PGME (1-methoxy- 2-Propanol, ie propylene glycol monomethyl ether), glycol ether solvents such as 3-methoxy-3-methyl-1-butanol; ethylene glycol monomethyl ether acetate, PGMEA (propylene glycol monomethyl ether acetate), diethylene glycol monobutyl ether acetate, diethylene glycol Glycolester solvents such as monoethyl ether acetate; such as DMF (N, N-dimethylformamide), DEF (N, N-diethylformamide), DMAc (N, N-dimethylacetamide), NMP (N-methylpyrrolidone), etc. At least one selected from amide-based solvents; etc. can be used. Among these solvents, it is preferable to use an alcohol solvent or a glycol ether solvent, among which methanol, ethanol, butanol, IPA (isopropyl alcohol) or PGME (1-methoxy-2-propanol, that is, propylene glycol monomethyl). It is more preferable to use ether). The content of the surface-coated inorganic particles is preferably 0.1 to 95 parts by mass (that is, 0.1 parts by mass or more and 95 parts by mass or less) with respect to 100 parts by mass of the organic solvent, and is preferably 10 to 90 parts by mass (that is, 0.1 parts by mass or more and 95 parts by mass or less). That is, 10 parts by mass or more and 90 parts by mass or less) is more preferable, and 15 to 90 parts by mass (that is, 15 parts by mass or more and 90 parts by mass or less) is further preferable.

Next, a coating composition containing the surface-coated inorganic particles, an organic solvent, and a resin, or a coating composition containing the organic solvent dispersion and a resin will be described. As the organic solvent, the above-mentioned one can be used. Any resin can be used as the resin, and for example, a soluble type in a low-polarity non-aqueous solvent, an emulsion type, a colloidal dispersion type, and the like can be used without limitation. The resin types include polyester resin, urethane-modified polyester resin, epoxy-modified polyester resin, various modified polyester resins such as acrylic-modified polyester, polyether urethane resin, polycarbonate urethane resin, vinyl chloride-vinyl acetate copolymer, and epoxy resin. , Phenolic resin, acrylic resin, polyamideimide, polyimide, ethyl cellulose, hydroxyethyl cellulose, nitrocellulose, cellulose-acetate-butyrate (CAB), cellulose-acetate-propionate (CAP) and other modified celluloses; polyethylene glycol; polyethylene oxide, etc. Can be mentioned. The blending amount of the resin is preferably in the range of about 0.5 to 100 parts by mass with respect to 100 parts by weight of the surface-coated inorganic particles, more preferably in the range of about 1 to 50 parts by mass, and in the case of about 2 to 25 parts by mass. More preferred.

Specifically, as the resin, for example, B-309, B-310, M-430, M-406, M-460, M-1100 (manufactured by Toa Synthetic Co., Ltd.) of the Aronix (registered trademark) series; Light acrylate (registered trademark). ) Series MTG-A, DPM-A, THF-A, IB-XA, HOA-HH (N), 1,6HX-A, 1,9ND-A, PE-3A, PE-4A (manufactured by Kyoeisha Chemical Co., Ltd.) ); Epolite (trade name) series 40E, 4000, 3002 (N) (manufactured by Kyoeisha Chemical Co., Ltd.); NK Ester (registered trademark) series A-TMM-3, A-9550, A-DPH (Shin-Nakamura Chemical Co., Ltd.) KAYARAD (registered trademark) series DPHA, DPEA-12, DPCA-60 (manufactured by Nippon Kayaku Co., Ltd.) and the like.

The above-mentioned organic solvent dispersion or coating composition can be applied or sprayed on a substrate to form a layer of surface-coated inorganic particles, which can be cured if necessary. When titanium oxide fine particles are used as the surface-coated inorganic particles, a titanium oxide layer having high hardness and high visible light transmission can be formed, and can be used as a hard coat, a high refractive index layer, and an ultraviolet shielding layer. The base material is not particularly limited, and glass, plastic, ceramic, metal and the like can be used. The film thickness and the like can be set as appropriate.

The surface-coated inorganic particles are intramolecularly composed of a silicate compound having an amino group and / or a hydrolysis product thereof prepared in advance in the presence of the inorganic particles, preferably in the presence of an organic solvent containing the inorganic particles or an aqueous solvent. A reaction product with a compound having one α, β-unsaturated carbonyl group can be mixed, and the reaction product can be coated on the surface of the inorganic particles. This mixing may be as simple as mixing and stirring at room temperature, but with heat the coating proceeds faster. It is preferably carried out in the range of room temperature to 150 ° C. for 10 minutes to 20 hours. Mixing while dispersing is preferable because the coating proceeds further. A known disperser can be used when the dispersal is performed. Specific examples include a sand mill, a homogenizer, a ball mill, a paint shaker, and an ultrasonic disperser. Coating also proceeds by hydrolyzing the alkoxy groups of the reactants, but this hydrolysis reaction requires a certain amount of water and is 0.5-1.5 with respect to the hydrolyzable groups of the silicate. Equivalent (ie, 0.5 equivalents or more and 1.5 equivalents or less) is added. Further, in order to promote the hydrolysis reaction, an acid or an alkali may be added as a catalyst. In this way, the surface-coated inorganic particles can be produced, and a dispersion in which the surface-coated inorganic particles are dispersed in an organic solvent can also be produced. Alternatively, the silicate compound having an amino group and / or its hydrolysis product and the compound having an α, β-unsaturated carbonyl group are mixed in advance in a solvent-free system to cause a partial reaction. Then, by adding the surface-coated inorganic particles to the organic solvent together with the inorganic particles, a dispersion in which the surface-coated inorganic particles are dispersed in the organic solvent can be produced.

Alternatively, the surface-coated inorganic particles are intramolecularly composed of a silicate compound having an amino group and / or a hydrolysis product thereof in the presence of the inorganic particles, preferably in an organic solvent or an aqueous solvent containing the inorganic particles. Can be mixed with a compound having one α, β-unsaturated carbonyl group and reacted to coat the surface of the inorganic particles with the reaction product. This mixing may be carried out by simply mixing and stirring at room temperature in the same manner as described above, but the reaction proceeds faster when heat is applied. It is preferably carried out in the range of room temperature to 150 ° C. for 10 minutes to 20 hours. Mixing while dispersing is preferable because the coating proceeds further. A known disperser can be used when the dispersal is performed. Specific examples include a sand mill, a homogenizer, a ball mill, a paint shaker, and an ultrasonic disperser. Coating also proceeds by hydrolyzing the alkoxy groups of the reactants, but this hydrolysis reaction requires a certain amount of water and is 0.5-1.5 with respect to the hydrolyzable groups of the silicate. Equivalent (ie, 0.5 equivalents or more and 1.5 equivalents or less) is added. Further, in order to promote the hydrolysis reaction, an acid or an alkali may be added as a catalyst. In this way, the surface-coated inorganic particles can be produced, and a dispersion in which the surface-coated inorganic particles are dispersed in an organic solvent can also be produced.

In the present invention, it can be produced by the above method, but in order to produce more advanced surface-coated inorganic particles, it is preferable to include the following first step and second step.
(First step)
In an aqueous solvent, the inorganic particles are mixed with the silicate compound having an amino group and / or the hydrolysis product thereof, and the surface of the inorganic particles is coated with the silicate compound having an amino group and / or the hydrolysis product thereof. It is a process.
(Second step)
Next, after replacing the aqueous solvent with an organic solvent, a compound having one α, β-unsaturated carbonyl group in the molecule is mixed, and a silicate compound having an amino group coated on the surface of the inorganic particles. And / or a step of coating the surface of the inorganic particles with a reaction product of the hydrolysis product thereof and the above-mentioned compound having an α, β-unsaturated carbonyl group.

First, in the first step, the inorganic particles and the silicate compound having an amino group and / or the hydrolysis product thereof are mixed in an aqueous solvent to produce the silicate compound having an amino group and / or the hydrolysis product thereof. A substance can be adsorbed on the surface of the inorganic particles, precipitated, or reacted to coat the surface of the inorganic particles. If necessary, the pH may be adjusted or the silicate compound may be hydrolyzed. The aqueous solvent may contain water or an organic solvent that dissolves in water. When the inorganic particles and the silicate compound having an amino group and / or its hydrolysis product are mixed in an aqueous solvent, the inorganic particles are suspended or dispersed using a normal suspender or disperser. It is preferable to prepare a liquid. Inorganic particles may be previously suspended or dispersed in an aqueous solvent using a normal suspender or disperser, and the aqueous dispersion is mixed with a silicate compound having an amino group and / or a hydrolysis product thereof. You can also. The content of the inorganic particles in the aqueous solvent can be appropriately set. This mixing may be carried out by simply mixing and stirring at room temperature in the same manner as described above, but the reaction proceeds faster when heat is applied. It is preferably carried out in the range of room temperature to heating / reflux temperature for 10 minutes to 20 hours. Mixing while dispersing is preferable because the coating proceeds further. A known disperser can be used when the dispersal is performed. Specific examples include a sand mill, a homogenizer, a ball mill, a paint shaker, and an ultrasonic disperser. Coating also proceeds by hydrolyzing the alkoxy groups of the reactants, but this hydrolysis reaction requires a certain amount of water and is 0.5-1.5 with respect to the hydrolyzable groups of the silicate. Equivalent (ie, 0.5 equivalents or more and 1.5 equivalents or less) is added. Further, in order to promote the hydrolysis reaction, an acid or an alkali may be added as a catalyst. Both the suspension and the dispersion liquid represent a state in which the fine particles are dispersed in the liquid, but it is generally understood that the suspension is easier for the fine particles to settle than the dispersion liquid. However, in the present specification, for convenience, the suspension and the dispersion liquid are not particularly distinguished, and the suspension is also referred to as a dispersion liquid.

Next, in the second step, the aqueous solvent is replaced with an organic solvent, and the inorganic particles are suspended or dispersed in the organic solvent. The replacement method can be performed by a conventionally known method such as centrifugation, decantation, or flushing. As a preferred method, the surfactant and the organic solvent are mixed with the above-mentioned aqueous solvent containing the inorganic particles coated with the silicate compound having an amino group and / or the hydrolysis product thereof, and the inorganic particles are precipitated, if necessary. After solid-liquid separation, the inorganic particles are transferred to an organic solvent. As the surfactant, an anionic surfactant (anionic surfactant) is preferable, and when dissociated in water, it becomes an anion, and a silicate compound having an amino group coated in the first step and / or a hydrolysis product thereof. The inorganic particles are coagulated and precipitated by neutralizing. Examples of the surfactant include monoalkyl sulfate (ROSO ₃ ^- M ⁺ ), alkylpolyoxyethylene sulfate (RO (CH ₂ CH ₂ O) _m SO ₃ ^- M ⁺ ), and alkylbenzene sulfonate (RCH ₂ CHC _6). Examples thereof include H ₄ SO ₃ ^- M ⁺ ) and monoalkyl phosphate (ROPO (OH) O ^- M ⁺ ), but dialkyl sulfosuccinates such as di (2-ethylhexyl) sodium sulfosuccinate are preferable. The above R represents an alkyl chain having 12 to 15 carbon atoms (that is, 12 or more and 15 or less), m is an integer of 1 to 150 (that is, 1 or more and 150 or less), and M is an alkali metal or an alkaline earth metal. At least one selected from. For the solid-liquid separation, a conventionally known method can be used, a method such as centrifugation, filtration, or ultrafiltration can be used, and excess silicate compounds, surfactants, etc. can be removed, which is necessary. It may be washed accordingly. Further, after recovering the precipitated inorganic particles by solid-liquid separation, heat treatment (drying) at a temperature of 80 to 200 ° C. (that is, 80 ° C. or higher and 200 ° C. or lower) causes a silicate compound having an amino group and / or hydrolysis thereof. It is more preferable because the decomposition product is more firmly coated on the surface of the inorganic particles. A more preferable temperature is 100 to 160 ° C. (that is, 100 ° C. or higher and 160 ° C. or lower). Next, the solid-liquid separated inorganic particles or the heat-treated inorganic particles are suspended or dispersed in an organic solvent using a suspender or a disperser to obtain a dispersion. The content of the inorganic particles can be set as appropriate. As the organic solvent, the above-mentioned solvent can be appropriately used. The organic solvent preferably does not contain water, and the water content is preferably 1% by mass or less.

Next, after dispersing the above-mentioned silicate compound having an amino group and / or inorganic particles coated with a hydrolysis product thereof in an organic solvent, a compound having one α, β-unsaturated carbonyl group in the molecule is added. The surface of the inorganic particles is coated with a reaction product of the silicate compound having an amino group and / or its hydrolysis product and the compound having an α, β-unsaturated carbonyl group described above by mixing and reacting.

When a compound having one α, β-unsaturated carbonyl group in the molecule is mixed with the organic solvent dispersion of inorganic particles coated with the silicate compound having an amino group and / or its hydrolysis product, this compound is obtained. Reacts with a silicate compound having an amino group and / or a hydrolysis product thereof, which is coated on the surface of the inorganic particles, and the produced reactant is coated on the surface of the inorganic particles. A silicate having an amino group coated on the surface of the inorganic particle and / or a hydrolysis product thereof is bonded to an α, β-unsaturated carbonyl compound to form a silicate having an alkyl chain having a long carbon number on the surface of the inorganic particle. Compounds can be synthesized. The compound having an α, β-unsaturated carbonyl group to be reacted is preferably a compound having one α, β-unsaturated carbonyl group in the molecule and having an ether bond in the molecule. As a compound having an ether bond, an ethylene glycol chain having a polymerization number of n = 2 to 10 (that is, 2 or more and 10 or less), a propylene glycol chain having a polymerization number of n = 2 to 10 (that is, 2 or more and 10 or less) or 5 to Compounds having a 6-membered cyclic group are more preferable, and (meth) acrylates or alkoxypolyalkylene glycol (meth) acrylates having a 5- to 6-membered cyclic group (that is, a 5- or 6-membered cyclic group) are further preferable.

The compound having an α, β-unsaturated carbonyl group may be mixed by simply mixing and stirring at room temperature in the same manner as described above, but the reaction proceeds faster when heat is applied. It is preferably carried out in the range of room temperature to heating / reflux temperature for 10 minutes to 20 hours. Mixing while dispersing is preferable because the coating proceeds further. A known disperser can be used when the dispersal is performed. Specific examples include a sand mill, a homogenizer, a ball mill, a paint shaker, and an ultrasonic disperser. In this way, the surface-coated inorganic particles can be produced, and a dispersion in which the surface-coated inorganic particles are dispersed in an organic solvent can also be produced. When the amino group of the silicate compound having an amino group and / or its hydrolysis product is a mol, and the compound having an α, β-unsaturated carbonyl group is b mol, 0.8 ≦ a / b. It is preferably ≦ 10, more preferably 1 ≦ a / b ≦ 10, more preferably 1 ≦ a / b ≦ 8, and most preferably 1 ≦ a / b ≦ 6.

In the present invention, in order to produce a more advanced organic solvent dispersion, it is preferable to include the following third and fourth steps.
(Third step)
This is a step of adding a poor solvent to the organic solvent dispersion obtained in the second step, separating the solid and liquid, and recovering the surface-coated inorganic particles.
(Fourth step)
Next, it is a step of dispersing the recovered surface-coated inorganic particles in an organic solvent.

In the third step, a poor solvent is added to the organic solvent in which the surface-coated inorganic particles produced in the second step are suspended, and solid-liquid separation is performed to recover the surface-coated inorganic particles. For the solid-liquid separation, a conventionally known method can be used, and the surface-coated inorganic particles are recovered by a method such as centrifugation, filtration, or ultrafiltration. When a poor solvent is mixed with the organic solvent in which the surface-coated inorganic particles are dispersed, the surface-coated inorganic particles aggregate and precipitate, so that solid-liquid separation becomes easy. The poor solvent can be appropriately selected, and a polar solvent such as alcohol or a non-polar solvent such as hexane, benzene or petroleum ether may be used. The amount of the poor solvent added can be appropriately set as long as the surface-coated inorganic particles aggregate. The agglomerated surface-coated inorganic particles can be solid-liquid separated, separated from an organic solvent and a poor solvent, excess compounds and the like can be removed, and may be washed and dried as necessary. The drying temperature can be appropriately set, preferably 80 to 200 ° C. (that is, 80 ° C. or higher and 200 ° C. or lower), and a more preferable temperature is 100 to 160 ° C. (that is, 100 ° C. or higher and 160 ° C. or lower). Is.

In the fourth step, the recovered surface-coated inorganic particles are mixed with an organic solvent and dispersed in the organic solvent. After the third step, the solid-liquid separated surface-coated inorganic particles (including the solid-liquid separated and then dried inorganic particles) can be suspended or dispersed in an organic solvent to produce an organic solvent dispersion. can. The above-mentioned organic solvent can be used, and a known suspender or disperser can be used as the means for suspending or dispersing.

An organic solvent dispersion can be produced by mixing the surface-coated inorganic particles produced as described above with an organic solvent. Further, the coating composition can be produced by mixing the surface-coated inorganic particles, the organic solvent, and the resin, or by mixing the resin with the organic solvent dispersion. A known suspender or disperser can be used for mixing. Additives such as a dispersant may be appropriately added to the organic solvent dispersion and the coating composition. A surface-coated inorganic particle layer can be produced by applying or spraying an organic solvent dispersion or a coating composition of surface-coated inorganic particles thus produced onto a substrate. The base material is not particularly limited, and glass, plastic, ceramic, metal and the like can be used. A layer of surface-coated inorganic particles can be formed on the substrate and cured if necessary. Curing can be appropriately carried out by a conventional method, preferably drying at a temperature of 50 to 200 ° C. (that is, 50 ° C. or higher and 200 ° C. or lower), and 80 to 150 ° C. (that is, 80 ° C. or higher and 150 ° C. or lower). Drying at this temperature is more preferred. The curing time can be set as appropriate. In addition, the film thickness and the like can be set as appropriate.

Examples and comparative examples are shown below, but the present invention is not limited to these examples.

[Example 1]
In an aqueous solution obtained by mixing 0.48 g of 3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-903, hereinafter referred to as "KBM-903"), 29.76 g of ion-exchanged water, and 0.16 g of acetic acid. , 1.6 g of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd .: TTO-51A) and 98 g of 0.05 mm zirconia beads were added and dispersed in a bead mill. After removing the beads, the supernatant was recovered by centrifugation _{to obtain a titanium oxide aqueous dispersion (TiO 2} concentration 5%) treated with 3-aminopropyltrimethoxysilane.

Next, 3.76 g of dioctylsodium sulfosuccinate (manufactured by Sigma-Aldrich Japan Co., Ltd .: hereinafter referred to as "DSS") dissolved in 40 g of toluene was added to 80 g of the obtained aqueous dispersion, left overnight, and then subjected to solvent replacement. bottom. A Dean-Stark apparatus was attached, and dehydration heating was performed at an oil bath temperature of 140 ° C. for 4 hours _{to obtain a toluene dispersion of titanium oxide treated with 3-aminopropyltrimethoxysilane (adjusted to a TiO 2} concentration of 10%).

Next, 10 g of 1-methoxy-2-propanol, that is, propylene glycol monomethyl ether (hereinafter referred to as "PGME") was added to 10 g of the obtained toluene dispersion, and then 0.183 g of methoxy-triethylene glycol acrylate (Kyoeisha Co., Ltd.) Chemical Co., Ltd .: Light acrylate (registered trademark) MTG-A (hereinafter referred to as "MTG-A") and 0.339 g of triethylamine (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) were added, and the mixture was stirred at 65 ° C. for 24 hours. After completion of stirring, 40 g of petroleum ether (poor solvent) was added, and the precipitate was recovered by centrifugation. PGME was added to the precipitate and dispersed to obtain PGME dispersion 1.

[Example 2]
Example 1 and Example 1 except that 0.183 g of methoxy-polyethylene glycol acrylate (manufactured by Kyoeisha Chemical Co., Ltd .: light acrylate (registered trademark) 130A, hereinafter referred to as "130A") was used instead of MTG-A. The same operation was carried out to obtain PGME dispersion 2.

[Example 3]
In Example 1, the same operation as in Example 1 was performed except that the amount of MTG-A added was 0.061 g and N, N-dimethylacetamide (hereinafter referred to as “DMAc”) was used instead of PGME. , DMAc dispersion 3 was obtained.

[Example 4]
In a solution obtained by mixing 0.225 g of KBM-903, 0.275 g of MTG-A, and 37.5 g of PGME, 2 g of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd .: TTO-51A) and 65 g of 0.1 mm zirconia beads Was put in and dispersed in a bead mill. After removing the beads, centrifugation was performed and the supernatant was recovered to obtain PGME dispersion 4.

[Example 5]
Titanium oxide was mixed with 0.235 g of KBM-903, 0.265 g of methoxydipropylene glucol acrylate (manufactured by Kyoeisha Chemical Co., Ltd .: light acrylate (registered trademark) DPM-A), and 37.5 g of PGME. 2 g (manufactured by Ishihara Sangyo Co., Ltd .: TTO-51A) and 65 g of 0.1 mm zirconia beads were added and dispersed by a bead mill. After removing the beads, centrifugation was performed and the supernatant was recovered to obtain PGME dispersion 5.

[Example 6]
2 g of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd .: TTO-51A) and 65 g of 0.1 mm zirconia beads were added to a solution obtained by mixing 0.135 g of KBM-903, 0.365 g of 130A, and 37.5 g of PGME. Dispersion treatment was performed with a bead mill. After removing the beads, centrifugation was performed and the supernatant was recovered to obtain PGME dispersion 6.

[Example 7]
2 g of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd .: TTO-51A) and 65 g of 0.1 mm zirconia beads were added to a solution obtained by mixing 0.213 g of KBM-903, 0.287 g of 130A, and 37.5 g of PGME. Dispersion treatment was performed with a bead mill. After removing the beads, centrifugation was performed to collect the supernatant to obtain PGME dispersion 7.

[Example 8]
Put 2 g of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd .: TTO-51A) and 65 g of 0.1 mm zirconia beads in a mixed solution of 0.427 g of KBM-903, 0.173 g of MTG-A, and 37.4 g of DMAc, and bead mill. Distributed processing with. After removing the beads, centrifugation was performed and the supernatant was recovered to obtain a DMAc dispersion 8.

[Example 9]
A bead mill containing 2 g of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd .: TTO-51A) and 65 g of 0.1 mm zirconia beads in a solution obtained by mixing 0.316 g of KBM-903, 0.284 g of 130A, and 37.4 g of DMAc. Distributed processing with. After removing the beads, centrifugation was performed and the supernatant was recovered to obtain a DMAc dispersion 9.

[Example 10]
A bead mill containing 2 g of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd .: TTO-51A) and 65 g of 0.1 mm zirconia beads in a solution obtained by mixing 0.414 g of KBM-903, 0.186 g of 130A, and 37.4 g of DMAc. Distributed processing with. After removing the beads, centrifugation was performed and the supernatant was recovered to obtain a DMAc dispersion 10.

[Example 11]
Zirconium oxide 2 g (manufactured by Daiichi Rare Element Chemical Industry Co., Ltd .: UEP-100), 0.1 mm zirconia beads 65 g in a solution obtained by mixing 0.316 g of KBM-903, 0.284 g of 130A, and 37.4 g of DMAc. Was put in and dispersed in a bead mill. After removing the beads, centrifugation was performed and the supernatant was recovered to obtain a DMAc dispersion 11.

[Comparative Example 1]
Mix 0.6 g of 3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-903) and 37.4 g of DMAc, and add 2 g of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd .: TTO-51A) to the mixed solution. 65 g of 0.1 mm zirconia beads were added and dispersed in a bead mill. After removing the beads, centrifugation was performed to recover the supernatant, but the entire amount of titanium oxide was precipitated.

[Reference Example 1]
_{The titanium oxide aqueous dispersion (TiO 2} concentration 5%) prepared in Example 1 treated with 3-aminopropyltrimethoxysilane was used as a reference sample as a reference for the dispersibility evaluation.

The particle size distribution was measured in Examples 1 to 11 and Reference Example 1.

[Measurement of particle size distribution]
Using a dynamic light scattering (DLS: Dynamic Light Scattering) particle size distribution measuring device (Microtrac Bell, Inc .: Nanotrac® Wave2 UZ152), the particle size distribution of inorganic particles in the dispersion is measured. , Cumulative particle size distributions D10, D50, D90 were measured. The results are shown in Table 1. As described above, a / b described in Table 1 contains a molar amino group of a silicate compound having an amino group in the reaction product and / or a hydrolysis product thereof, and the above-mentioned α, β-non. It represents the molar ratio of the compound having an α, β-unsaturated carbonyl group to the amino group when the compound having a saturated carbonyl group is b mol. In Examples 1 to 3, since "solvent substitution" was performed, the amount of the silicate compound having an amino group and / or its hydrolysis product and the compound having an α, β-unsaturated carbonyl group were charged. There is a discrepancy between the a / b obtained from the charged amount and the actual a / b. Therefore, for a / b of Examples 1 to 3, the obtained organic solvent dispersions were subjected to thermogravimetric analysis, and the calculated values calculated from the amount of mass loss are shown in Table 1.

In the dispersions of Examples 1 to 11, the value of D50 of the particle size distribution is around 40 nm or less, which is not much different from that of the aqueous dispersion of Reference Example 1, and is therefore the same as that of the aqueous dispersion of Reference Example 1. It was also found that it was sufficiently dispersed even in an organic solvent.

[Example 12]
8.4 g of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd .: TTO-51N) and 65 g of 0.1 mm zirconia beads were added to a solution obtained by mixing 0.445 g of KBM-903, 1.225 g of 130A, and 21.92 g of PGME. , Dispersion treatment with a bead mill. After removing the beads, centrifugation was performed and the supernatant was recovered to obtain a PGME dispersion 12.

[Example 13]
To the solution obtained by mixing 0.716 g of KBM-903, 0.964 g of 130A, and 21.92 g of PGME, 8.4 g of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd .: TTO-51N) and 65 g of 0.1 mm zirconia beads were added. It was put in and dispersed in a bead mill. After removing the beads, centrifugation was performed and the supernatant was recovered to obtain a PGME dispersion 13.

[Example 14]
8.4 g of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd .: TTO-51N) and 65 g of 0.1 mm zirconia beads were added to the solution obtained by mixing 0.885 g of KBM-903, 0.795 g of 130A, and 21.92 g of PGME. It was put in and dispersed in a bead mill. After removing the beads, centrifugation was performed and the supernatant was recovered to obtain a PGME dispersion 14.

[Example 15]
To the solution obtained by mixing 1.092 g of KBM-903, 0.558 g of 130A and 21.92 g of PGME, 8.4 g of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd .: TTO-51N) and 65 g of 0.1 mm zirconia beads were added. , Dispersion treatment with a bead mill. After removing the beads, centrifugation was performed and the supernatant was recovered to obtain a PGME dispersion 15.

[Example 16]
To the solution obtained by mixing 1.324 g of KBM-903, 0.356 g of 130A, and 21.92 g of PGME, 8.4 g of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd .: TTO-51N) and 65 g of 0.1 mm zirconia beads were added. , Dispersion treatment with a bead mill. After removing the beads, centrifugation was performed and the supernatant was recovered to obtain a PGME dispersion 16.

[Example 17]
After mixing 1.079 g of KBM-903, 0.601 g of 130A, and 21.92 g of PGME, 8.4 g of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd .: TTO-V5) and 65 g of 0.1 mm zirconia beads are added to this solution. , Dispersion treatment with a bead mill. After removing the beads, centrifugation was performed and the supernatant was recovered to obtain a PGME dispersion 17.

[Example 18]
After mixing 0.885 g of KBM-903, 0.795 g of 130A, and 21.92 g of PGME, 8.4 g of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd .: TTO-V5) and 65 g of 0.1 mm zirconia beads are added to this solution. , Dispersion treatment with a bead mill. After removing the beads, centrifugation was performed and the supernatant was recovered to obtain a PGME dispersion 18.

[Example 19]
After mixing 1.092 g of KBM-903, 0.558 g of 130A, and 21.92 g of PGME, 8.4 g of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd .: TTO-V5) and 65 g of 0.1 mm zirconia beads were added to this solution. It was put in and dispersed in a bead mill. After removing the beads, centrifugation was performed and the supernatant was recovered to obtain PGME dispersion 19.

[Example 20]
A mixture of 0.789 g of KBM-903, 0.891 g of methoxydipropylene glucol acrylate (manufactured by Kyoeisha Chemical Co., Ltd .: light acrylate (registered trademark) DPM-A, hereinafter referred to as "DPM-A"), and 21.92 g of PGME. After that, 8.4 g of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd .: TTO-V5) and 65 g of 0.1 mm zirconia beads were added to this solution, and dispersion treatment was performed with a bead mill. After removing the beads, centrifugation was performed and the supernatant was recovered to obtain a PGME dispersion 20.

[Example 21]
8.4 g of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd .: TTO-V5), 65 g of 0.1 mm zirconia beads in a solution obtained by mixing 0.959 g of KBM-903, 0.721 g of DPM-A, and 21.92 g of PGME. Was put in and dispersed in a bead mill. After removing the beads, centrifugation was performed and the supernatant was recovered to obtain a PGME dispersion 21.

[Example 22]
8.4 g of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd .: TTO-51N), 65 g of 0.1 mm zirconia beads in a solution obtained by mixing 0.959 g of KBM-903, 0.721 g of DPM-A, and 21.92 g of PGME. Was put in and dispersed in a bead mill. After removing the beads, centrifugation was performed and the supernatant was recovered to obtain a PGME dispersion 22.

[Example 23]
Titanium oxide 8.4 g (manufactured by Ishihara Sangyo Co., Ltd .: TTO-V5), 0.1 mm zirconia beads 65 g in a solution obtained by mixing 1.221 g of KBM-903, 0.459 g of DPM-A, and 21.92 g of PGME. Was put in and dispersed in a bead mill. After removing the beads, centrifugation was performed and the supernatant was recovered to obtain a PGME dispersion 23.

[Example 24]
A mixture of 1.063 g of KBM-903, 0.617 g of tetrahydrofurfuryl acrylate (manufactured by Kyoeisha Chemical Co., Ltd .: light acrylate (registered trademark) THF-A, hereinafter referred to as "THF-A"), and 21.92 g of PGME. 8.4 g of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd .: TTO-V5) and 65 g of 0.1 mm zirconia beads were added to the obtained solution and dispersed in a bead mill. After removing the beads, centrifugation was performed and the supernatant was recovered to obtain a PGME dispersion 24.

[Example 25]
After mixing 0.927 g of KBM-903, 0.753 g of MTG-A, and 21.92 g of PGME, 8.4 g of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd .: TTO-V5) and 65 g of 0.1 mm zirconia beads were mixed in this solution. Was put in and dispersed with a bead mill. After removing the beads, centrifugation was performed and the supernatant was recovered to obtain a PGME dispersion 25.

[Example 26]
8.4 g of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd .: TTO-V5) in a solution obtained by mixing 0.883 g of KBM-903, 0.797 g of DPM-A, and 21.92 g of PGMEA (propylene glycol monomethyl ether acetate). , 0.1 mm zirconia beads (65 g) were added and dispersed in a bead mill. After removing the beads, centrifugation was performed and the supernatant was recovered to obtain PGMEA dispersion 26.

[Example 27]
8.4 g of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd .: TTO-V5) and 0. 65 g of 1 mm zirconia beads were added and dispersed in a bead mill. After removing the beads, centrifugation was performed and the supernatant was recovered to obtain an ethanol dispersion 27.

[Example 28]
A solution obtained by mixing 0.959 g of KBM-903, 0.721 g of DPM-A, and 21.92 g of isopropyl alcohol (IPA) was mixed with 8.4 g of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd .: TTO-V5) and 0. .65 g of 1 mm zirconia beads were added and dispersed in a bead mill. After removing the beads, centrifugation was performed and the supernatant was recovered to obtain an isopropyl alcohol dispersion 28.

[Example 29]
After mixing 0.883 g of KBM-903, 0.797 g of DPM-A, and 21.92 g of methyl ethyl ketone (MEK), 8.4 g of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd .: TTO-V5) and 0. 65 g of 1 mm zirconia beads were added and dispersed in a bead mill. After removing the beads, centrifugation was performed and the supernatant was recovered to obtain a methyl ethyl ketone dispersion 29.

[Comparative Example 2]
A solution obtained by mixing 1.030 g of KBM-903, 0.650 g of 1,6-hexanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: light acrylate (registered trademark) 1,6HX-A), and 21.92 g of PGM. 8.4 g of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd .: TTO-V5) and 65 g of 0.1 mm zirconia beads were placed therein and dispersed in a bead mill. After removing the beads, centrifugation was performed to recover the supernatant, but the entire amount of titanium oxide was precipitated.

[Comparative Example 3]
8.4 g of titanium oxide in a solution obtained by mixing 0.539 g of KBM-903, 1.141 g of PEG600 # diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: light acrylate (registered trademark) 14EG-A), and 21.92 g of PGME. (Ishihara Sangyo Co., Ltd .: TTO-V5), 0.1 mm zirconia beads (65 g) were added and dispersed with a bead mill. After removing the beads, centrifugation was performed to recover the supernatant, but the entire amount of titanium oxide was precipitated.

[Comparative Example 4]
1.083 g of KBM-903, 0.650 g of trimethylolpropane triacrylate (manufactured by Toagosei Co., Ltd .: Aronix (registered trademark) M-309), and 21.92 g of PGME were mixed to obtain 8.4 g of titanium oxide. (Ishihara Sangyo Co., Ltd .: TTO-V5), 0.1 mm zirconia beads (65 g) were added and dispersed with a bead mill. After removing the beads, centrifugation was performed to recover the supernatant, but the entire amount of titanium oxide was precipitated.

Table 2 shows the dispersion states in Examples 12 to 29 and Comparative Examples 2 to 4. Table 2 shows a case where the dispersed state was good, a case where the solid content was dispersed but a concentration crack of 5% or more was indicated by Δ, and a case where the solid content was not dispersed was indicated by ×. The α, β-unsaturated carbonyl compounds in Table 2 include mono-α, β-unsaturated carbonyl compounds having one C = C bond in the molecule in Examples 12 to 29 (Examples 12 to 29). That is, a compound having one α, β-unsaturated carbonyl group in the molecule) is used, and in Comparative Examples 2 to 4, another di or triunsaturated carbonyl having 2 to 3 C = C bonds in the molecule is used. A compound was used.

[Paint preparation 1]
4 g of each titanium dioxide fine particle (TTO-51N) -containing organic solvent dispersion obtained in Examples 12 to 16 and Example 22, 0.25 g of dipentaerythritol hexaacrylate (manufactured by Toagosei Co., Ltd .: M-405), urethane. 0.25 g of acrylate (manufactured by Toagosei Co., Ltd .: M-1200), 0.025 g of IRGACURE (registered trademark) -184, 0.4 g of diacetone alcohol, leveling agent (manufactured by Shin-Etsu Chemical Co., Ltd .: KY-1203) 0.04 g was mixed, and each curable coating composition was prepared so that the refractive index of the film was 1.8 to 1.82.

[Paint preparation 2]
4 g of each titanium dioxide fine particle (TTO-V5) -containing organic solvent dispersion obtained in Examples 17 to 21, 23 to 29 and Comparative Examples 2 to 4, dipentaerythritol hexaacrylate (manufactured by Toagosei Co., Ltd .: M-405) 0.21 g, urethane acrylate (manufactured by Toagosei Co., Ltd .: M-1200) 0.21 g, IRGACURE (registered trademark) -184 0.021 g, diacetone alcohol 0.4 g, leveling agent (manufactured by Shin-Etsu Chemical Co., Ltd.) : KY-1203) was mixed, and each curable coating composition was prepared so that the refractive index of the film was 1.8 to 1.82.

[Measurement of refractive index of film]
Each of the above-prepared curable coating compositions is applied to a glass substrate as a coating liquid prepared as a paint, pre-dried at 150 ° C. for 5 minutes, and then cured by irradiating with a high-pressure mercury lamp to cure the curable coating composition. Three films with different film thicknesses were formed for each object. The haze of the obtained coating film was measured with a haze meter (NDH-7000 manufactured by Nippon Denshoku Kogyo Co., Ltd.), and the film thickness of the coating film and the refractive index at the measurement wavelength of 589 nm were measured with an ellipsometer (manufactured by SmartSE Horiba, Ltd.). The film thickness and the HAZE value were plotted, and the HAZE value with a film thickness of 3 μm was calculated by linear approximation and shown in Table 2.

[Reference Example A]
It was obtained by mixing 0.827 g of 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-803, hereinafter referred to as "KBM-803"), 0.853 g of DPM-A, and 21.92 g of PGME. 8.4 g of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd .: TTO-V5) and 65 g of 0.1 mm zirconia beads were added to the solution and dispersed in a bead mill. The molar ratio of KBM-803 to DPM-A is 1: 1. After removing the beads, centrifugation was performed to collect the supernatant to obtain PGME dispersion A. When the dispersed state was measured in the same manner as described above, the state was Δ. Moreover, when the HAZE value of the film thickness of 3 μm was calculated, it was 1.43.

[Reference Example B]
8.4 g of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd .: TTO-V5) and 0.1 mm zirconia beads were mixed in a solution obtained by mixing 0.827 g of KBM-803, 0.853 g of DPM-A, and 21.92 g of PGMEA. 65 g was added and dispersed with a bead mill. The molar ratio of KBM-803 to DPM-A is 1: 1. After removing the beads, centrifugation was performed to collect the supernatant to obtain PGMEA dispersion B. When the dispersed state was measured in the same manner as described above, the state was ◯. Moreover, when the HAZE value of the film thickness of 3 μm was calculated, it was 1.19.

The present invention is a surface-coated inorganic particle coated with a reaction product of a silicate compound having an amino group and / or a hydrolysis product thereof and a compound having one α, β-unsaturated carbonyl group in the molecule. , The dispersibility of the inorganic particles in the organic solvent can be sufficiently improved, whereby the functions and performances of the inorganic particles can be fully exhibited. Further, the organic solvent dispersion and the coating film of the obtained surface-coated inorganic particles can be made excellent in transparency and refraction.

Claims

A surface-coated inorganic particle in which the surface of an inorganic particle is coated with a reaction product of a silicate compound having an amino group and / or a hydrolysis product thereof and a compound having one α, β-unsaturated carbonyl group in the molecule.
The surface-coated inorganic particles according to claim 1, wherein the compound having an α, β-unsaturated carbonyl group is a compound having an ether bond.
The compound having an α, β-unsaturated carbonyl group is an ethylene glycol chain (polymerization number n = 2 to 10), a propylene glycol chain (polymerization number n = 2 to 10), or a compound having a 5 to 6-membered cyclic group. The surface-coated inorganic particles according to claim 1 or 2.
Any of claims 1 to 3, wherein the compound having an α, β-unsaturated carbonyl group is a (meth) acrylate having a 5- to 6-membered cyclic group or an alkoxypolyalkylene glycol (meth) acrylate. Surface-coated inorganic particles described in Crab.
The compound according to any one of claims 1 to 4, wherein the compound having an α, β-unsaturated carbonyl group is tetrahydrofurfuryl acrylate, methoxytriethylene glycol acrylate, methoxypolyethylene glycol acrylate or methoxydipropylene glycol acrylate. The surface-coated inorganic particles described.
When the amino group of the silicate compound having an amino group and / or its hydrolysis product in the reaction product is a mol, and the compound having an α, β-unsaturated carbonyl group is b mol, 0.8 ≦ The surface-coated inorganic particle according to any one of claims 1 to 5, wherein a / b ≦ 10.
The surface-coated inorganic particles according to any one of claims 1 to 6, wherein the reaction product is a small molecule silicate compound having 3 to 100 carbon atoms and / or a hydrolysis product thereof.
The surface-coated inorganic particles according to any one of claims 1 to 7, wherein the inorganic particles are composed of inorganic core particles and an inorganic compound coated on the surface thereof.
Surface-coated inorganic particles in which the inorganic particles according to any one of claims 1 to 7 or the inorganic core particles according to claim 8 are titanium oxide particles.
An organic solvent dispersion of surface-coated inorganic particles in which the surface-coated inorganic particles according to any one of claims 1 to 9 are dispersed in an organic solvent.
A coating composition containing the surface-coated inorganic particles according to any one of claims 1 to 9, an organic solvent, and a resin.
A coating composition containing the organic solvent dispersion according to claim 10 and a resin.
The inorganic particles are mixed with the silicate compound having an amino group and / or the hydrolysis product thereof in an aqueous solvent, and the surface of the inorganic particles is coated with the silicate compound having an amino group and / or the hydrolysis product thereof. The first step and
Next, after replacing the aqueous solvent with an organic solvent, a compound having one α, β-unsaturated carbonyl group in the molecule is mixed, and the silicate compound having an amino group coated on the surface of the inorganic particles and the silicate compound. / Or a second step of coating the surface of the inorganic particles with a reaction product of the hydrolysis product thereof and the compound having an α, β-unsaturated carbonyl group.
A method for producing surface-coated inorganic particles including.
In the second step, the surfactant and the organic solvent are mixed with the aqueous solvent, the inorganic particles are transferred to the organic solvent, the organic solvent is replaced with the aqueous solvent, and then the α, β-unsaturated carbonyl is used. The method for producing a surface-coated inorganic particle according to claim 13, wherein a compound having a group is mixed.
A silicate compound having an amino group is obtained by mixing an inorganic particle, a silicate compound having an amino group and / or a hydrolysis product thereof, and a compound having one α, β-unsaturated carbonyl group in the molecule. And / or a method for producing a surface-coated inorganic particle, wherein the reaction product of the hydrolysis product thereof and the compound having an α, β-unsaturated carbonyl group is coated on the surface of the inorganic particle.
When the amino group of the silicate compound having an amino group and / or its hydrolysis product is a mol, and the compound having an α, β-unsaturated carbonyl group is b mol, 0.8 ≦ a / b. The method for producing a surface-coated inorganic particle according to any one of claims 13 to 15, wherein ≦ 10.
A third step of adding a poor solvent to the organic solvent dispersion obtained in the second step of claim 13 or claim 14, solid-liquid separation, and recovering the surface-coated inorganic particles.
Next, a fourth step of dispersing the recovered surface-coated inorganic particles in an organic solvent, and
A method for producing an organic solvent dispersion of surface-coated inorganic particles containing.
In an organic solvent, inorganic particles, a silicate compound having an amino group and / or a hydrolysis product thereof, and a compound having one α, β-unsaturated carbonyl group in the molecule are mixed to form the above amino. A surface coating in which a reaction product of a silicate compound having a group and / or a hydrolysis product thereof and the compound having an α, β-unsaturated carbonyl group is coated on the surface of inorganic particles and dispersed in the organic solvent. A method for producing an organic solvent dispersion of inorganic particles.
When the amino group of the silicate compound having an amino group and / or its hydrolysis product is a mol, and the compound having an α, β-unsaturated carbonyl group is b mol, 0.8 ≦ a / b. The method for producing an organic solvent dispersion according to claim 18, wherein ≦ 10.
A method for producing a surface-coated inorganic particle layer, wherein the organic solvent dispersion of the surface-coated inorganic particles according to claim 10 or the coating composition according to claim 11 or 12 is applied or sprayed onto a substrate.